Reactions of simple aromatic heterocycles with niobium cluster ions (n < or = 30)

The Journal of Chemical Physics
Britta PfefferGereon Niedner-Schatteburg

Abstract

Prior work on benzene activation by size selected niobium cluster cations and anions of up to 30 atoms is extended systematically through studying aromatic poly- and heterocyclic molecules such as naphthalene, pyridine, thiophene, pyrrole, furan, and benzofuran. Naphthalene is found to act much like benzene when reacting under single collision conditions with individual clusters. The most likely process is carbidization through complete dehydrogenation. Some clusters of particular sizes (most notably n=19) fail to activate both homocyclic molecules. Instead seemingly intact adsorption is observed which proves that activation is kinetically hindered at some point. All of the five studied heterocyclic aromatic molecules react unconditionally and by complete dehydrogenation with cationic niobium clusters, while they only attach to or react with anionic clusters larger than a minimum size of n=19-21. These findings are taken as strong evidence for initial coordination to the metal clusters of the heterocycles through their lone pair orbitals. The paper comprehends the observations in terms of cluster surface structure and reactivity.

References

Dec 26, 2001·Chemical Reviews·G Frenking, N Fröhlich
Nov 5, 2002·Current Opinion in Chemical Biology·Sason ShaikDetlef Schröder
Mar 12, 2004·Annual Review of Physical Chemistry·M B Knickelbein
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Citations

Nov 17, 2017·The Journal of Chemical Physics·Jennifer MohrbachGereon Niedner-Schatteburg
Jun 13, 2012·The Journal of Physical Chemistry. a·Pham Vu Nhat, Minh Tho Nguyen
Dec 20, 2012·The Journal of Physical Chemistry. a·Matthias TombersGereon Niedner-Schatteburg

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Methods Mentioned

BETA
differential scanning calorimetry

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